Patent GB-1025793-A (GB)
Title: Improvements in and relating to sulfines and polymers produced therefrom
IPC: C08L33/20
Filed: 1962-08-01
Abstract: Homopolymers and copolymers of certain specified ethylenically unsaturated sulphines are used as flocculating agents.ALSO:The invention comprises sulphines of formula <FORM:1025793/C2/1> where R is H or Me, R1 is a saturated aliphatic hydrocarbon radicle of 1-4 C atoms, R11 is an alkyl radicle of 1-4 C atoms, R111 is Me or CH2COOH, X is methylsulphate or Hlg, X being Cl when R111 is CH2COOH, and m is 1 or 2. Preferably, R1 has 2 or 3 C atoms and is unsubstituted in the position adjacent to the O atom, R11 has 1 or 2 C atoms and when m is 1 the sulphonium radicle is attached to the C atom of R1 which is farthest from O, and when m is 2 R1 has at least 3 C atoms and the sulphonium radicles are attached to vicinal C atoms especially hose farthest from O.  The sulphines are made by treating an appropriate thioether with an alkylating agent, e.g. in a solvent at 25-100 DEG C. in the presence of a polymerization inhibitor.  Preferably, the solvent is a non-solvent for the product, e.g. benzene and isopropyl ether. Examples illustrate the preparation of the sulphines, representative being (2-acryloxyethyl) carboxymethyl methyl sulphonium chloride and methyl sulphate and 3-methacryloxypropyl-1,2-bis-(carboxymethylmethyl - sulphonium) dichloride. The products may be polymerized or copolymerized (see Division C3) or may be used as textile assistants or foaming, wetting or emulsifying agents.ALSO:The invention comprises polymers of sulphines of formula <FORM:1025793/C3/1> where R is a hydrogen atom or a methyl radical, R1 is a saturated aliphatic hydrocarbon radical of 1-4 carbon atoms, R11 is an alkyl radical of 1-4 carbon atoms, R111 is a methyl radical or a carboxymethyl radicle, X is a methylsulphate radical or halogen atom, X being chlorine when R111 is carboxymethyl, and m is 1 or 2 and includes copolymers of the sulphines with thioethers of formula <FORM:1025793/C3/2> where R, R1, R11 and m are as above and copolymers containing, in polymerized form, on a theoretical monomer basis, at least 5 mole per cent, preferably 50 to 95 mole per cent, of the sulphine with an alpha-ethylenically unsaturated comonomer of acrylonitrile, a vinyl alkanoate in which the acid moiety has 2 to 8 carbon atoms, an alkyl or cyanoalkyl acrylate or methacrylate of formula <FORM:1025793/C3/3> where R is as above and R1111 is an alkyl or cyanoalkyl radical of 1 to 8 carbon atoms or acrylamide.  The invention also includes terpolymers of the sulphine with an alphaethylenically unsaturated thio-ether and one of the above alpha-ethylenically unsaturated comonomers but excluding acrylamide.  The terpolymers contain, in polymerized form, on a theoretical monomer basis, at least 10 mole per cent, preferably at least 50 mole per cent of the sulphine, when taken together with the amount of polymerized thio-ether and at least 5 mole per cent, preferably from 50 to 95 mole per cent, of the sulphine based on the total amount of polymerized monomers.  The invention further comprises terpolymers containing, in polymerized form, and on a theoretical monomer basis, from 20 to 95 mole per cent of acrylamide and 5 to 80 mole per cent of a mixture containing at least 50 mole per cent of the sulphine together with the thioether. A mixture of sulphines may be used.  Polymerization is effected in the usual way preferably in acetonitrile solution at - 10 DEG  to 120 DEG  C. in the presence of free radical polymerization catalysts. Polymer products obtained in acetone, acetonitrile or a mixture of these solvents, or a constant boiling methyl acetate-methanol mixture by dissolving the monomers in these diluents in a preferred concentration of 5 to 30 per cent by weight of total monomer, based upon the weight of the polymerization charge, yield a high molecular weight, granular product; polymer products obtained from water or dimethyl formamide are in the form of a clear gel and those from benzene, heptane and ethylene dichloride are of lower molecular weight.  In an alternative polymerization method the alkylation of the thio-ether (see Division C2) and the polymerization of the monomers may be carried out simultaneously, the alkylating agent being used in a mole ratio of at least 0.1: 1, preferably at least 0.5: 1 to 5: 1, with regard to the alpha-ethylenically unsaturated thio-ether.  The polymers may also be obtained by alkylating an initially formed polymer.  The products are used in the preparation of films for packaging and coatings and are of particular use as an ingredient in fibre-forming polymer compositions, e.g. those of acrylonitrile, which show enhanced dye affinity.  The water-soluble polymers containing, in polymerized form, on a theoretical monomer basis, at least 50 mole per cent of sulphine can be used as flocculents for aqueous anionic suspensions, e.g. slurries of silica, carbon black, clay, textile mill wastes, bleached sulphite pulp wastes, and sewage sludge (see Division C1).  Examples illustrated the preparation of the various products and their use in fibres. Representative of sulphines polymerized are (2 - acryloxyethyl) carboxymethylmethyl sulphonium chloride and methyl sulphate and 3-methacryloxypropyl-1,2-bis-(carboxymethylmethyl-sulphonium) dichloride.